US5918103A - Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy - Google Patents

Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy Download PDF

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US5918103A
US5918103A US08/693,343 US69334396A US5918103A US 5918103 A US5918103 A US 5918103A US 69334396 A US69334396 A US 69334396A US 5918103 A US5918103 A US 5918103A
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tungsten carbide
carbide
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hard alloy
tungsten
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Masaki Kobayashi
Kozo Kitamura
Satoshi Kinoshita
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Tungaloy Corp
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Toshiba Tungaloy Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/055—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component

Definitions

  • the present invention relates to a hard alloy having excellent hardness, toughness, wear resistance, fracture resistance, plastic deformation resistance and thermal cracking resistance, in which plate-crystalline tungsten carbide (hereinafter abbreviated to "platy WC”) is crystallized.
  • the platy WC is crystallized to a platy WC-containing hard alloy suitable as cutting tools such as an insert, a drill and an end mill, a base material of a coating super hard tool, plastic working tools such as a drawing mold, a die mold and a forging mold and shearing tools such as a punching mold and a slitter.
  • the present invention also relates to a composition for forming platy WC and a process for preparing the platy WC-containing hard alloy.
  • hardness i.e., wear resistance and strength and toughness, i.e., fracture resistance of a hard alloy
  • hardness i.e., wear resistance and strength and toughness, i.e., fracture resistance of a hard alloy
  • toughness i.e., fracture resistance of a hard alloy
  • platy WC has a shape represented by a triangular plate or a hexagonal plate and has a (001) face preferentially grown in the direction of the (001) face since the (001) face of WC crystal shows the highest hardness, whereas the direction of a (100) face shows the highest elastic modulus, is desirable.
  • the growing rate of the (001) crystal face of WC is low, all of the a axis length, c axis length and c/a ratio of the WC crystal are small and the ratio of platy WC contained therein is low.
  • said processes can be applied only to a hard alloy in which compositional components are limited, and preparation cost is high.
  • An object of the present invention is to provide a platy WC-containing hard alloy which exhibits a synergistic effect by high hardness, high toughness and high strength such that hardness is high, wear resistance is excellent, toughness if high and also fracture resistance is excellent. This synergism cannot be obtained in a conventional hard alloy.
  • achieving a long lifetime by heightening all of the growing rate of a WC (001) crystal face, the a axis length, c axis length and c/a ratio of WC (001) crystal and the ratio of platy WC crystal contained is also an object.
  • platy WC-forming powder comprising composite carbide containing an iron group metal, W and C or a precursor thereof and carbon powder is also an object of the present invention.
  • the present inventors have studied for many years in order to improve the strength, toughness and fracture resistance of a hard alloy without lowering hardness and wear resistance thereof. Consequently the inventors found that such an object can be achieved by heightening all of the growing rate of a WC (001) crystal face, the a axis length, c axis length and c/a ratio of WC (001) crystal and the ratio of platy WC crystal contained in the alloy.
  • carbon powder is added to composite carbide comprising an iron group metal, W and C or powder of a precursor which forms this composite carbide during heating. The mixture is then heated and platy WC satisfying the characteristics described above can be easily formed by reaction and crystallization, to accomplish the present invention.
  • the platy WC-containing hard alloy of the present invention is a hard alloy which comprises (a) 4 to 40% by volume of a binder phase containing at least one of iron group metals (cobalt (Co), nickel (Ni) and iron (Fe)) as a main component; and (b) the balance of a hard phase comprising (i) tungsten carbide, or (ii) tungsten carbide containing 50% by volume or less of a compound with a cubic structure selected from at least one of carbide and nitride of the 4a (titanium (Ti), zirconium (Zr) and hafnium (Hf)), 5a (vanadium (V), niobium (Nb) and tantalum (Ta)) or 6a (chromium (Cr), molybdenum (Mo) and tungsten (W)) group element of the periodic table and mutual solid solutions thereof, and inevitable impurities,
  • the platy WC-containing hard alloy of the present invention has three features described below.
  • the binder phase of the platy WC-containing hard alloy of the present invention there may be specifically mentioned, for example, Co, Ni, Fe, and alloys such as Co--Ni, Co--W, Ni--Cr and Fe--Ni--Cr. If the amount of the binder phase is less than 4% by volume, sintering becomes difficult so that cavities remain in an inner portion, or the rate of forming platy WC crystal is lowered so that strength and hardness are remarkably lowered. On the other hand, if the amount exceeds 40% by volume, the amount of WC including plate crystal is relatively decreased so that hardness and wear resistance are remarkably lowered.
  • the compound with a cubic structure in the platy WC-containing hard alloy of the present invention there may be specifically mentioned, for example, TaC, NbC, V 4 C 3 , VC, (W,Ti)C, (W,Ti,Ta)C, TiN, ZrN, (W,Ti)(C,N) and (W,Nb,Zr)CN. If the amount of the compound with a cubic structure exceeds 50% by volume, the amount of WC including platy WC is relatively decreased so that hardness and toughness are remarkably lowered.
  • the platy WC-containing hard alloy comprises 4 to 40% by volume of the binder phase containing at least one of iron group metals (Co, Ni and Fe) as a main component.
  • the balance is WC.
  • peak intensities at a (001) face and a (101) face in X-ray diffraction using Cu--K ⁇ rays are represented by h(001) and h(101), respectively, said WC satisfies h(001)/h(101) ⁇ 0.50. If the peak intensity ratio of h(001)/h(101) is less than 0.50, the growing rate of the WC (001) crystal face showing the highest hardness is low, whereby improvement of hardness if small.
  • the peak intensity ratio of h(001)/h(101) is preferably 0.55 or more, particularly preferably 0.60 or more.
  • the platy WC-containing hard alloy has a feature that the WC crystal has an a axis length of 0.2907 nm or more and a c axis length of 0.2840 nm or more. If the a axis length is less than 0.2907 nm or the c axis length is less than 0.2840 nm, inner distortion of a WC crystal lattice is small, whereby an effect of increasing hardness is small.
  • the platy WC-containing hard alloy of the present invention has a feature that the ratio of the c axis length to the a axis length of the crystalline axis, i.e., the c/a ratio is particularly preferably 0.9770 or more.
  • the platy WC-containing hard alloy has a feature that the (001) face of the WC crystal is oriented parallel to a pressurized face in a molding step to exhibit orientation property. That is, when the peak intensities at the (001) face and the (101) face of the WC crystal by X-ray diffractometry of a face p parallel to said pressurized face and a face h perpendicular thereto are represented by p(001), p(101), h(001) and h(101), respectively, p(001)/p(101)>1.2 ⁇ h(001)/h(101) is satisfied. If this relative peak intensity ratio does not satisfy the above formula, the orientation rate of the WC (001) face in a specific direction is decreased to lower anisotrophy of hardness, which is not suitably used for exhibiting properties by improving hardness in a specific direction or face.
  • the platy WC-containing hard alloy described above preferably contains 20% by volume or more of platy WC having a ratio of the maximum length to the minimum length of a WC particle in a sectional structure of the WC particle being 3.0 or more. This results in all of the various characteristics such as hardness, wear resistance, strength, toughness and fracture resistance being improved. It is particularly preferred depending on the case that the average particle size of WC is 0.5 ⁇ m or less.
  • Platy WC in the sectional structure of the hard alloy is contained preferably in an amount of 40% by volume or more, particularly preferably 50% by volume or more.
  • the composition for forming platy WC to be used for preparing the platy WC-containing hard alloy of the present invention comprises composite carbide containing 60 to 90% by weight of W, 0.5 to 3.0% by weight of carbon and the balance of at least one of iron group metals, whereby a hard alloy having a high content of platy WC can be obtained.
  • composite carbide there may be specifically mentioned, for example, Co 3 W 9 C 4 , Co 2 W 4 C, Co 3 W 3 C, Co 6 W 6 C, Ni 2 W 4 C, Fe 2 W 4 C, Fe 3 W 3 C, Fe 4 W 2 C and mutual solid solutions thereof.
  • the process for preparing the platy WC-containing hard alloy of the present invention comprises molding mixed powder of platy WC-forming powder which comprises composite carbide comprising an iron group metal, W and C and/or a precursor thereof, carbon powder and, if necessary, cubic compound-forming powder.
  • the molded compact is then sintered by heating at 1,200 to 1,600° C. under vacuum or non-oxidizing atmosphere.
  • the process of the present invention is carried out under the same conditions as in a conventional process for preparing a hard alloy, for example, for a sintering-maintaining time of 30 to 90 minutes under atmosphere of a non-oxidizing gas such as an inert gas or hydrogen gas under reduced pressure, normal pressure or pressurization.
  • the composite carbide in the process for preparing the platy WC-containing hard alloy of the present invention is the same as the composite carbide described above. Further, there may be mentioned composites in which 20% by weight of less of the 4a, 5a or 6a group metal (excluding W) of the periodic table is dissolved in the above composite carbide such as Co 3 (W,Ti) 9 C 4 , Co 2 (W,V) 4 C, Co 3 (W,Ta) 3 C, (Ni,Cr) 2 W 4 C and (Fe,Mo) 3 W 3 C.
  • the dissolved 4a, 5a or 6a group metal is preferred in some cases since it has an action of controlling the size, shape and distribution of crystallized platy WC particles simultaneously with forming carbide by sintering under heating.
  • the precursor of the composite carbide in the process for preparing the platy WC-containing hard alloy of the present invention there may be specifically mentioned a W alloy containing an iron group metal, a mixture of W and/or W 2 C and an iron group metal and a mixture of WC, an oxide of the 4a, 5a or 6a group metal of the periodic table and an iron group metal.
  • powder of an alloy of W-10% by weight of Co mixed powder of W 2 C-10% by weight of Co, mixed powder of WC-10% by weight of TiO 2 -10% by weight of Co and mixed powder of W-10% by weight of WC-2% by weight of Cr 2 O 3 -10% by weight of Ni, each of which reacts with a part of carbon powder added during sintering under heating to form the above composite carbide.
  • the carbon source compound in the process for preparing the platy WC-containing hard alloy of the present invention there may be specifically mentioned graphite, thermal carbon, petroleum pitch and a thermosetting resin.
  • graphite Particularly when powder of the precursor of the above composite carbide is used, it is preferred to use graphite having an average particle size of 2 to 20 ⁇ m since formation of platy WC is accelerated to increase hardness and toughness.
  • the amount of carbon may be any amount so long as it is an amount sufficient for reducing residual oxygen mixed in the powder by sintering under heating; and is also capable of forming a platy WC with a W component. Also, it is present in such an amount that the composite carbide does not remain or free carbon is not precipitated in the hard alloy obtained by sintering.
  • the cubic compound-forming powder to be added may include, for example, TaC, NbC, V 4 C 3 , VC, TiC, (W,Ti)C, (W,Ti,Ta)C, TiN, ZrN and Ti(CN).
  • the sintering under heating in the process for preparing the platy WC-containing hard alloy of the present invention includes: a first stage of forming composite carbide represented by W 3-X W 3+X C (where M represents an iron group metal and 0 ⁇ X ⁇ 1); and a second stage of forming platy WC from said composite carbide since formation of platy WC is accelerated to increase hardness and toughness.
  • W alloy powder and/or metal W powder is/are contained as the above precursor since the WC (001) face in the hard alloy obtained is oriented in a specific direction to improve anisotrophy of hardness. That is, the flat faces of the W alloy powder and/or metal W powder which are made flat by mixing and pulverization are oriented parallel to a pressurized face in the molding step so that the (001) face of WC formed by sintering under heating is oriented parallel to the pressurized face.
  • the platy WC-containing hard alloy of the present invention has the action of improving hardness, strength, toughness and fracture resistance of an alloy simultaneously by the growing rate of a WC (001) crystal face, the a axis length, c axis length and c/a ratio of WC (001) crystal and the ratio of platy WC crystal contained therein.
  • the process for preparing the same has an action of forming platy WC and a binder phase by reacting composite carbide comprising an iron group metal, W and C with carbon.
  • the respective powders of commercially available W having average particle sizes of 0.5 ⁇ m, 1.5 ⁇ m and 3.2 ⁇ m shown as "W/F”, “W/M” and “W/L", respectively, in the following tables
  • carbon black with a size of 0.02 ⁇ m shown as “C” in the tables
  • Co, Ni, Fe, Cr, Cr 3 Cr 2 and TaH 2 with a size of 1 to 2 ⁇ m were weighed in accordance with the formulation compositions shown in Table 1 and charged into pots made of stainless steel together with an acetone solvent and balls made of a hard alloy.
  • the powders were mixed and pulverized for 24 hours and then dried to prepare mixed powders.
  • composition powders P(1) to P(6) of the present invention and precursors P(7) and P(8) were charged into graphite crucibles and heated under vacuum where atmospheric pressure was about 10 Pa for 1 hour at temperatures shown in Table 1 to prepare composition powders P(1) to P(6) of the present invention and precursors P(7) and P(8). After these powders were fixed by X-ray diffraction, compositions and components were quantitated by the internal addition method. The results are shown in Table 1.
  • composition powders in Table 1 and the respective powders of the above W, C, Co, Ni, Fe, Cr and Cr 3 C 2 , commercially available WC having average particle sizes of 0.5 ⁇ m, 1.5 ⁇ m, and 3.2 ⁇ m shown as “WC/F”, “WC/M” and “WC/L”, respectively, in the tables
  • W 2 C with a size of 1.4 ⁇ m
  • graphite with a size of 6.0 ⁇ m (shown as “G” in the tables)
  • WO 3 with a size of 0.4 ⁇ m
  • the powders were mixed and pulverized for 48 hours and then dried to prepare mixed powders.
  • the mixed powders were charged into metal molds and pressurized under a pressure of 2 ton/cm 2 to prepare green compact molds each having a size of about 5.5 ⁇ 9.5 ⁇ 29 mm.
  • the green compact molds were placed on sheets comprising alumina and carbon fiber, heated under vacuum where atmospheric pressure was about 10 Pa and maintained for 1 hour at temperatures shown in Table 2 to obtain hard alloys of Present samples 1 to 17 and Comparative samples 1 to 17.
  • the hard alloy samples thus obtained were subjected to wet grinding processing using #230 diamond grinding stone to prepare samples each having a size of 4.0 ⁇ 8.0 ⁇ 25.0 mm.
  • Each of the sample's flexural strength (strength resistant to bending) was measured (by a method corresponding to Japanese Industrial Standard B4104 which is similar to ISO 242, 2804).
  • the Vickers hardness and a fracture toughness value K1c were measured with a load of 198 N (by the so-called IM method in which measurement is carried out by measuring length of cracks formed from an edge of dent by using a Vickers hardness tester).
  • a structure photograph of the face subjected to lapping was taken by an electron microscope.
  • the average particle size of WC and the volume ratio of platy WC having a ratio of the maximum size to the minimum size of 3.0 or more to the whole WC were determined. Further, the ratio of the peak intensity at the (001) face of WC to the peak intensity at the (101) face of WC in X-ray diffraction using Cu--K ⁇ rays, and the lattice constant (a axis length, c axis length) and c/a ratio of the WC crystal were measured. The results are shown in Table 3.
  • Green compact molds of Present samples 1, 6, 7, 9, 10, 11, 15 and 16 and Comparative samples 1, 6, 7, 9, 10 and 13 used in Example 1 were heated by the same method and under the same conditions as in Example 1, maintained at the respective temperatures of 950° C. and 1,100° C. for 5 minutes, cooled and then taken out.
  • approximate compositions thereof were determined by the internal addition method by X-ray diffraction. The results are shown in Table 4.
  • the hard alloy samples thus obtained were subjected to wet grinding processing using #230 diamond grinding stone, and one face of the upper and lower faces (shown as “p face” in Table 5) and one face the side faces (shown as “h face” in Table 5) of the samples were subjected to lapping with 1 ⁇ m of diamond paste.
  • the peak intensity ratio of the (001) face to the (101) of the WC crystal by X-ray diffraction was measured. Further, as to the respective peak intensity ratios obtained, the ratio of the p face to the face was calculated. The results are shown in Table 5.
  • the platy WC-containing hard alloys of the present invention exhibit flexural strength, hardness and fracture toughness all of which are higher than those of the comparative hard alloys comprising the same components.
  • FC350 As used in the following examples, the designations "FC350”, “S48C” and “SKD11” have the following compositions.
  • the surfaces of the chips were coated successively with 1.0 ⁇ m of TiN, 5.0 ⁇ m of TiCN, 2.0 ⁇ m of TiC, 2.0 ⁇ m of Al 2 O 3 and 1.0 ⁇ m TiN (total coating thickness: 11 ⁇ m).
  • an intermittent lathe turning test was conducted by using steel under the following conditions to measure a life time until a blade tip was broken or a flank wear amount became 0.35 mm. The results are shown in Table 6.
  • Processing liquid wet type (a water-soluble oily agent)
  • Powder to be molded ferrite
  • the hard alloy containing platy WC of the present invention has remarkably excellent effects in that it has a Vickers hardness of 500 or more at HV20 and a fracture toughness K1c of 0.5 MPa ⁇ m 1/2 or more as compared with a conventional hard alloy having the same composition and particle size.
  • the process for preparing the same has effects in that a hard alloy having a high content of platy WC and a controlled particle size can be prepared easily and inexpensively.
  • the beneficial effects of the hard alloy containing platy WC of the present invention can be expected when a covered hard alloy is prepared by covering the surface of the hard alloy of the present invention with a hard film comprising a single layer or a multilayer of at least one of carbide, nitride, oxycarbide and oxynitride of the 4a (Ti, Zr and Hf), 5a (V, Nb and Ta) or 6a (W, Mo and Cr) group element of the periodic table, oxide and nitride of Al and mutual solid solutions thereof, diamond, diamond-like carbon, cubic boronitride and hard boronitride.
  • a hard film comprising a single layer or a multilayer of at least one of carbide, nitride, oxycarbide and oxynitride of the 4a (Ti, Zr and Hf), 5a (V, Nb and Ta) or 6a (W, Mo and Cr) group element of the periodic table, oxide and nitride of Al and mutual solid solutions

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Abstract

Disclosed are a plate-crystalline tungsten carbide-containing hard alloy which comprises 4 to 40% by volume of a binder phase containing at least one of iron group metals selected from Co, Ni and Fe as a main component; and the balance of a hard phase comprising tungsten carbide alone, or tungsten carbide and 50% by volume or less of a compound with a cubic structure selected from at least one of carbide and nitride of the 4a (Ti, Zr and Hf), 5a (V, Nb and Ta) or 6a (Cr, Mo and W) group element of the periodic table and mutual solid solutions thereof, and inevitable impurities,
wherein when peak intensities at a (001) face and a (101) face in X-ray diffraction using Kα rays with Cu being a target are represented by h(001) and h(101), respectively, the tungsten carbide satisfies h(001)/h(101)≧0.50, a composition for forming a plate-crystalline tungsten carbide, and a process for preparing the plate-crystalline tungsten carbide-containing hard alloy.

Description

This is a divisional of application Ser. No. 08/470,002 filed Jun. 6, 1995, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to a hard alloy having excellent hardness, toughness, wear resistance, fracture resistance, plastic deformation resistance and thermal cracking resistance, in which plate-crystalline tungsten carbide (hereinafter abbreviated to "platy WC") is crystallized. Specifically the platy WC is crystallized to a platy WC-containing hard alloy suitable as cutting tools such as an insert, a drill and an end mill, a base material of a coating super hard tool, plastic working tools such as a drawing mold, a die mold and a forging mold and shearing tools such as a punching mold and a slitter. The present invention also relates to a composition for forming platy WC and a process for preparing the platy WC-containing hard alloy.
In general, hardness, i.e., wear resistance and strength and toughness, i.e., fracture resistance of a hard alloy can be changed by WC particle size, Co content and additional amounts of other carbides such that the hard alloy has been widely used for various purposes. However, there is a problem of antimony tendency that if wear resistance is heightened, fracture resistance is lowered, while if fracture resistance is heightened, wear resistance is lowered.
One course for solving this problem includes paying attention to the anisotrophy of mechanical characteristics due to the crystal faces of WC. Specifically, for example, a means relating to a platy WC containing hard alloy or a process for preparing the same, in which platy WC has a shape represented by a triangular plate or a hexagonal plate and has a (001) face preferentially grown in the direction of the (001) face since the (001) face of WC crystal shows the highest hardness, whereas the direction of a (100) face shows the highest elastic modulus, is desirable.
As representative examples of prior art techniques relating to platy WC, there may be mentioned Japanese Patent Publications No. 23049/1972 and No. 23050/1972 and Japanese Provisional Patent Publications No. 34008/1982, No. 47239/1990, No. 51408/1990, No. 138434/1990, No. 274827/1990 and No. 339659/1993.
In Japanese Patent Publications No. 23049/1972 and No. 23050/1972, a process is described for preparing a platy WC-containing hard alloy by using mixed powder which comprises colloidal tungsten carbide powder containing a porous agglomerate for growing platy WC and a powder of Fe, Ni, Co or an alloy thereof.
In Japanese Provisional Patent Publication No. 34008/1982, a process is described for preparing twin tungsten carbide in which (001) faces are bonded as a twin face. This is accomplished by adding a small amount of an iron group metal salt to mixed powder of strongly pulverized W and C and then carbonizing the mixture under heating.
Further, in Japanese Provisional Patent Publications No. 47239/1990 and No. 138434/1990, a process is described for preparing a hard alloy by using, as a starting material, a solid solution of (W,Ti,Ta)C in which tungsten carbide is contained in a super-saturated state and crystallizing platy WC at the time of sintering under heating.
Next, in Japanese Provisional Patent Publication No. 274827/1990, a process is described for preparing an anisotropic hard alloy by subjecting a used hard alloy to oxidation, reduction and then carbonization to obtain powder. The powder is then molded and the resulting molded compact is then subjected to sintering or hot pressing.
In addition, in Japanese Provisional Patent Publication No. 339659/1993, a process is described for preparing a hard alloy containing platy WC by subjecting mixed powder comprising WC with a size of 0.5 μm or less, 3 to 40% by weight of a compound with a cubic structure and 1 to 25% by weight of Co and/or Ni to sintering at 1,450° C. or higher.
In the hard alloys or the hard alloys obtained by the preparation processes described in these 8 publications, the growing rate of the (001) crystal face of WC is low, all of the a axis length, c axis length and c/a ratio of the WC crystal are small and the ratio of platy WC contained therein is low. This results in the problem that all of the various characteristics of the hard alloy, particularly hardness, wear resistance, strength, toughness and fracture resistance cannot be improved. Also, in the preparation processes, it is difficult to control a particle size, and to heighten the ratio of platy WC contained therein. In addition, said processes can be applied only to a hard alloy in which compositional components are limited, and preparation cost is high.
SUMMARY OF THE INVENTION
The present invention has solved the problems as described above. An object of the present invention is to provide a platy WC-containing hard alloy which exhibits a synergistic effect by high hardness, high toughness and high strength such that hardness is high, wear resistance is excellent, toughness if high and also fracture resistance is excellent. This synergism cannot be obtained in a conventional hard alloy. In addition, achieving a long lifetime by heightening all of the growing rate of a WC (001) crystal face, the a axis length, c axis length and c/a ratio of WC (001) crystal and the ratio of platy WC crystal contained is also an object. Providing a process for preparing the same, by which platy WC can be easily incorporated into a hard alloy by sintering under heating mixed powder of platy WC-forming powder comprising composite carbide containing an iron group metal, W and C or a precursor thereof and carbon powder is also an object of the present invention.
The present inventors have studied for many years in order to improve the strength, toughness and fracture resistance of a hard alloy without lowering hardness and wear resistance thereof. Consequently the inventors found that such an object can be achieved by heightening all of the growing rate of a WC (001) crystal face, the a axis length, c axis length and c/a ratio of WC (001) crystal and the ratio of platy WC crystal contained in the alloy. In order to obtain such a hard alloy, carbon powder is added to composite carbide comprising an iron group metal, W and C or powder of a precursor which forms this composite carbide during heating. The mixture is then heated and platy WC satisfying the characteristics described above can be easily formed by reaction and crystallization, to accomplish the present invention.
That is, the platy WC-containing hard alloy of the present invention is a hard alloy which comprises (a) 4 to 40% by volume of a binder phase containing at least one of iron group metals (cobalt (Co), nickel (Ni) and iron (Fe)) as a main component; and (b) the balance of a hard phase comprising (i) tungsten carbide, or (ii) tungsten carbide containing 50% by volume or less of a compound with a cubic structure selected from at least one of carbide and nitride of the 4a (titanium (Ti), zirconium (Zr) and hafnium (Hf)), 5a (vanadium (V), niobium (Nb) and tantalum (Ta)) or 6a (chromium (Cr), molybdenum (Mo) and tungsten (W)) group element of the periodic table and mutual solid solutions thereof, and inevitable impurities,
wherein when peak intensities at a (001) face and a (101) face in X-ray diffraction using Kα rays with Cu being a target are represented by h(001) and h(101), respectively, said tungsten carbide satisfies h(001)/h(101)≧0.50,
and the platy WC-containing hard alloy of the present invention has three features described below.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following, the present invention is explained in detail.
As the binder phase of the platy WC-containing hard alloy of the present invention, there may be specifically mentioned, for example, Co, Ni, Fe, and alloys such as Co--Ni, Co--W, Ni--Cr and Fe--Ni--Cr. If the amount of the binder phase is less than 4% by volume, sintering becomes difficult so that cavities remain in an inner portion, or the rate of forming platy WC crystal is lowered so that strength and hardness are remarkably lowered. On the other hand, if the amount exceeds 40% by volume, the amount of WC including plate crystal is relatively decreased so that hardness and wear resistance are remarkably lowered.
As the compound with a cubic structure in the platy WC-containing hard alloy of the present invention, there may be specifically mentioned, for example, TaC, NbC, V4 C3, VC, (W,Ti)C, (W,Ti,Ta)C, TiN, ZrN, (W,Ti)(C,N) and (W,Nb,Zr)CN. If the amount of the compound with a cubic structure exceeds 50% by volume, the amount of WC including platy WC is relatively decreased so that hardness and toughness are remarkably lowered.
In the first preferred embodiment of the present invention, the platy WC-containing hard alloy comprises 4 to 40% by volume of the binder phase containing at least one of iron group metals (Co, Ni and Fe) as a main component. The balance is WC. When peak intensities at a (001) face and a (101) face in X-ray diffraction using Cu--Kα rays are represented by h(001) and h(101), respectively, said WC satisfies h(001)/h(101)≧0.50. If the peak intensity ratio of h(001)/h(101) is less than 0.50, the growing rate of the WC (001) crystal face showing the highest hardness is low, whereby improvement of hardness if small. The peak intensity ratio of h(001)/h(101) is preferably 0.55 or more, particularly preferably 0.60 or more.
In the second preferred embodiment of the present invention, the platy WC-containing hard alloy has a feature that the WC crystal has an a axis length of 0.2907 nm or more and a c axis length of 0.2840 nm or more. If the a axis length is less than 0.2907 nm or the c axis length is less than 0.2840 nm, inner distortion of a WC crystal lattice is small, whereby an effect of increasing hardness is small. Further, the platy WC-containing hard alloy of the present invention has a feature that the ratio of the c axis length to the a axis length of the crystalline axis, i.e., the c/a ratio is particularly preferably 0.9770 or more.
In the third preferred embodiment of the present invention, the platy WC-containing hard alloy has a feature that the (001) face of the WC crystal is oriented parallel to a pressurized face in a molding step to exhibit orientation property. That is, when the peak intensities at the (001) face and the (101) face of the WC crystal by X-ray diffractometry of a face p parallel to said pressurized face and a face h perpendicular thereto are represented by p(001), p(101), h(001) and h(101), respectively, p(001)/p(101)>1.2×h(001)/h(101) is satisfied. If this relative peak intensity ratio does not satisfy the above formula, the orientation rate of the WC (001) face in a specific direction is decreased to lower anisotrophy of hardness, which is not suitably used for exhibiting properties by improving hardness in a specific direction or face.
The platy WC-containing hard alloy described above preferably contains 20% by volume or more of platy WC having a ratio of the maximum length to the minimum length of a WC particle in a sectional structure of the WC particle being 3.0 or more. This results in all of the various characteristics such as hardness, wear resistance, strength, toughness and fracture resistance being improved. It is particularly preferred depending on the case that the average particle size of WC is 0.5 μm or less. Platy WC in the sectional structure of the hard alloy is contained preferably in an amount of 40% by volume or more, particularly preferably 50% by volume or more.
The composition for forming platy WC to be used for preparing the platy WC-containing hard alloy of the present invention comprises composite carbide containing 60 to 90% by weight of W, 0.5 to 3.0% by weight of carbon and the balance of at least one of iron group metals, whereby a hard alloy having a high content of platy WC can be obtained. As said composite carbide, there may be specifically mentioned, for example, Co3 W9 C4, Co2 W4 C, Co3 W3 C, Co6 W6 C, Ni2 W4 C, Fe2 W4 C, Fe3 W3 C, Fe4 W2 C and mutual solid solutions thereof.
The process for preparing the platy WC-containing hard alloy of the present invention comprises molding mixed powder of platy WC-forming powder which comprises composite carbide comprising an iron group metal, W and C and/or a precursor thereof, carbon powder and, if necessary, cubic compound-forming powder. The molded compact is then sintered by heating at 1,200 to 1,600° C. under vacuum or non-oxidizing atmosphere. The process of the present invention is carried out under the same conditions as in a conventional process for preparing a hard alloy, for example, for a sintering-maintaining time of 30 to 90 minutes under atmosphere of a non-oxidizing gas such as an inert gas or hydrogen gas under reduced pressure, normal pressure or pressurization.
The composite carbide in the process for preparing the platy WC-containing hard alloy of the present invention is the same as the composite carbide described above. Further, there may be mentioned composites in which 20% by weight of less of the 4a, 5a or 6a group metal (excluding W) of the periodic table is dissolved in the above composite carbide such as Co3 (W,Ti)9 C4, Co2 (W,V)4 C, Co3 (W,Ta)3 C, (Ni,Cr)2 W4 C and (Fe,Mo)3 W3 C. The dissolved 4a, 5a or 6a group metal is preferred in some cases since it has an action of controlling the size, shape and distribution of crystallized platy WC particles simultaneously with forming carbide by sintering under heating.
As the precursor of the composite carbide in the process for preparing the platy WC-containing hard alloy of the present invention, there may be specifically mentioned a W alloy containing an iron group metal, a mixture of W and/or W2 C and an iron group metal and a mixture of WC, an oxide of the 4a, 5a or 6a group metal of the periodic table and an iron group metal. There may be more specifically mentioned, for example, powder of an alloy of W-10% by weight of Co, mixed powder of W2 C-10% by weight of Co, mixed powder of WC-10% by weight of TiO2 -10% by weight of Co and mixed powder of W-10% by weight of WC-2% by weight of Cr2 O3 -10% by weight of Ni, each of which reacts with a part of carbon powder added during sintering under heating to form the above composite carbide.
As the carbon source compound in the process for preparing the platy WC-containing hard alloy of the present invention, there may be specifically mentioned graphite, thermal carbon, petroleum pitch and a thermosetting resin. Particularly when powder of the precursor of the above composite carbide is used, it is preferred to use graphite having an average particle size of 2 to 20 μm since formation of platy WC is accelerated to increase hardness and toughness. The amount of carbon may be any amount so long as it is an amount sufficient for reducing residual oxygen mixed in the powder by sintering under heating; and is also capable of forming a platy WC with a W component. Also, it is present in such an amount that the composite carbide does not remain or free carbon is not precipitated in the hard alloy obtained by sintering.
In the process for preparing the platy WC-containing hard alloy of the present invention, the cubic compound-forming powder to be added, if necessary, may include, for example, TaC, NbC, V4 C3, VC, TiC, (W,Ti)C, (W,Ti,Ta)C, TiN, ZrN and Ti(CN).
It is preferred that the sintering under heating in the process for preparing the platy WC-containing hard alloy of the present invention includes: a first stage of forming composite carbide represented by W3-X W3+X C (where M represents an iron group metal and 0≦X≦1); and a second stage of forming platy WC from said composite carbide since formation of platy WC is accelerated to increase hardness and toughness.
In the process for preparing the platy WC-containing hard alloy of the present invention, it is preferred that W alloy powder and/or metal W powder is/are contained as the above precursor since the WC (001) face in the hard alloy obtained is oriented in a specific direction to improve anisotrophy of hardness. That is, the flat faces of the W alloy powder and/or metal W powder which are made flat by mixing and pulverization are oriented parallel to a pressurized face in the molding step so that the (001) face of WC formed by sintering under heating is oriented parallel to the pressurized face.
The platy WC-containing hard alloy of the present invention has the action of improving hardness, strength, toughness and fracture resistance of an alloy simultaneously by the growing rate of a WC (001) crystal face, the a axis length, c axis length and c/a ratio of WC (001) crystal and the ratio of platy WC crystal contained therein. The process for preparing the same has an action of forming platy WC and a binder phase by reacting composite carbide comprising an iron group metal, W and C with carbon.
EXAMPLES
The present invention is described in detail by referring to Examples.
EXAMPLE 1
First, the respective powders of commercially available W having average particle sizes of 0.5 μm, 1.5 μm and 3.2 μm (shown as "W/F", "W/M" and "W/L", respectively, in the following tables), carbon black with a size of 0.02 μm (shown as "C" in the tables) and Co, Ni, Fe, Cr, Cr3 Cr2 and TaH2 with a size of 1 to 2 μm were weighed in accordance with the formulation compositions shown in Table 1 and charged into pots made of stainless steel together with an acetone solvent and balls made of a hard alloy. The powders were mixed and pulverized for 24 hours and then dried to prepare mixed powders. The mixed powders were charged into graphite crucibles and heated under vacuum where atmospheric pressure was about 10 Pa for 1 hour at temperatures shown in Table 1 to prepare composition powders P(1) to P(6) of the present invention and precursors P(7) and P(8). After these powders were fixed by X-ray diffraction, compositions and components were quantitated by the internal addition method. The results are shown in Table 1.
Next, the composition powders in Table 1 and the respective powders of the above W, C, Co, Ni, Fe, Cr and Cr3 C2, commercially available WC having average particle sizes of 0.5 μm, 1.5 μm, and 3.2 μm (shown as "WC/F", "WC/M" and "WC/L", respectively, in the tables), W2 C with a size of 1.4 μm, graphite with a size of 6.0 μm (shown as "G" in the tables), WO3 with a size of 0.4 μm, TiO2 with a size of 0.03 μm and a (W,Ti,Ta)C solid solution (WC/TiC/TaC=50/20/30 in terms of weight ratio, shown as "WTT" in the tables) with a size of 1.5 μm were weighed in accordance with the formulation compositions shown in Table 2 and charged into pots made of stainless steel together with an acetone solvent and balls made of a hard alloy. The powders were mixed and pulverized for 48 hours and then dried to prepare mixed powders. The mixed powders were charged into metal molds and pressurized under a pressure of 2 ton/cm2 to prepare green compact molds each having a size of about 5.5×9.5×29 mm. The green compact molds were placed on sheets comprising alumina and carbon fiber, heated under vacuum where atmospheric pressure was about 10 Pa and maintained for 1 hour at temperatures shown in Table 2 to obtain hard alloys of Present samples 1 to 17 and Comparative samples 1 to 17.
The hard alloy samples thus obtained were subjected to wet grinding processing using #230 diamond grinding stone to prepare samples each having a size of 4.0×8.0×25.0 mm. Each of the sample's flexural strength (strength resistant to bending) was measured (by a method corresponding to Japanese Industrial Standard B4104 which is similar to ISO 242, 2804). Further, after one face (parallel to a pressurized face) of each sample was subjected to lapping with 1 μm of diamond paste, the Vickers hardness and a fracture toughness value K1c were measured with a load of 198 N (by the so-called IM method in which measurement is carried out by measuring length of cracks formed from an edge of dent by using a Vickers hardness tester). A structure photograph of the face subjected to lapping was taken by an electron microscope. By an image processor, the average particle size of WC and the volume ratio of platy WC having a ratio of the maximum size to the minimum size of 3.0 or more to the whole WC were determined. Further, the ratio of the peak intensity at the (001) face of WC to the peak intensity at the (101) face of WC in X-ray diffraction using Cu--Kα rays, and the lattice constant (a axis length, c axis length) and c/a ratio of the WC crystal were measured. The results are shown in Table 3.
Also, approximate compositions measured by the structure photographs described above are shown in Table 2.
                                  TABLE 1
__________________________________________________________________________
      Formulation composition
                    Heating tem-
                           Composition
Sample No.
      (% by weight) perature (°C.)
                           (% by weight)
__________________________________________________________________________
Present
      88.4W/M-9.1Co-2.5C
                    1,300  90Co.sub.3 W.sub.9 C.sub.4 -5Co.sub.2 W.sub.4
                           C-5WC
sample P(1)
Present
      85.5W/F-13.1Co-1.4C
                    1,100  90Co.sub.2 W.sub.4 C-5Co.sub.6 W.sub.6 C-5WC
sample P(2)
Present
      87.6W/M-8.0Ni-2.0Cr.sub.3 C.sub.2 -2.4C
                    1,300  100(Ni, Cr).sub.2 W.sub.4 C
sample P(3)
Present
      75.3W/M-23.1Co-1.6C
                    1,300  90Co.sub.3 W.sub.3 C-5Co.sub.2 W.sub.4 C-5WC
sample P(4)
Present
      75.0W/M-23.4Fe-1.6C
                    1,200  90Fe.sub.3 W.sub.3 C-5Fe.sub.4 W.sub.2 C-5WC
sample P(5)
Present
      86.5W/M-9.0Co-2.0TaH.sub.2 -2.5C
                    1,300  95Co.sub.3 (W, Ta).sub.9 C.sub.4 -10WC
Sample P(6)
Sample P(7)
      90.0W/L-10.0Co
                    1,400  65W-35W.sub.6 Co.sub.7
Sample P(8)
      88.0W/F-2.0Cr-10.0Ni
                    1,100  85(W--Cr)-15WNi.sub.4
__________________________________________________________________________

                                  TABLE 2
__________________________________________________________________________
                             Sintering
           Formulation composition
                             tempera-
                                  Synthetic composition
Sample No. (% by weight)     ture (°C.)
                                  (% by weight)
__________________________________________________________________________
Present sample 1
           96.8P(1)-3.2C     1,400
                                  85.5WC-14.5Co
Present sample 2
           96.0P(2)-1.0Cr.sub.3 C.sub.2 -3.0C
                             1,380
                                  78.5WC-21.5(Co--Cr)
Present sample 3
           97.1P(3)-2.9C     1,420
                                  84.5WC-15.5(Ni--Cr)
Present sample 4
           96.8P(4)-3.2C     1,380
                                  66.5WC-33.5Co
Present sample 5
           96.7P(5)-3.3C     1,360
                                  64WC-36Fe
Present sample 6
           94.4P(7)-5.6G     1,400
                                  84.5WC-15.5Co
Present sample 7
           94.8P(8)-5.2G     1,420
                                  82WC-18(Ni--Cr)
Present sample 8
           67.1W.sub.2 C-30.0P(1)-2.9C
                             1,480
                                  95.5WC-4.5Co
Present sample 9
           59.2W.sub.2 C-30.0W/M-7.0Co-3.8G
                             1,420
                                  88.5WC-11.5Co
Present sample 10
           81.0WC/M-10.0WO.sub.3 -6.8Co-2.2Gr
                             1,420
                                  88.5WC-11.5Co
Present sample 11
           83.4W.sub.2 C-7.0Fe-5.0Ni-2.0Cr.sub.3 C.sub.2 -2.6C
                             1,420
                                  77WC-23(Fe--Ni--Cr)
Present sample 12
           96.8P(6)-3.2G     1,400
                                  83.5WC-2TaC-14.5Co
Present sample 13
           66.0P(1)-28.9W.sub.2 C-2.0TaC-3.1C
                             1,440
                                  88WC-2TaC-10Co
Present sample 14
           77.5P(1)-20.0WTT-2.5C
                             1,400
                                  63WC-26(W, Ti, Ta)C-11Co
Present sample 15
           68.5W/M-20.0WTT-7.0Co-4.5G
                             1,400
                                  63WC-26(W, Ti, Ta)C-11Co
Present sample 16
           79.8WC/M-5.4TiO.sub.2 -6.1TaC-7.1Co-1.7G
                             1,400
                                  63WC-26(W, Ti, Ta)C-11Co
Present sample 17
           58.1P(4)-40.0WTT-1.9C
                             1,440
                                  37WC-45(W, Ti, Ta)C-18Co
Comparative sample 1
           91.2WC/M-8.8Co    1,400
                                  85.5WC-14.5Co
Comparative sample 2
           86.5WC/F-1.0Cr.sub.3 C.sub.2 -12.7Co
                             1,380
                                  78.5WC-21.5(Co--Cr)
Comparative sample 3
           90.3WC/M-7.8Ni-1.9Cr.sub.3 C.sub.2
                             1,420
                                  84.5WC-15.5(Ni--Cr)
Comparative sample 4
           77.6WC/M-22.4Co   1,380
                                  66.5WC-33.5Co
Comparative sample 5
           77.4WC/M-22.6Fe   1,360
                                  64WC-36Fe
Comparative sample 6
           90.5WC/L-9.5Co    1,400
                                  84.5WC-15.5Co
Comparative sample 7
           88.6WC/F-1.8Cr.sub.3 C.sub.2 -9.6Ni
                             1,420
                                  82WC-18(Ni--Cr)
Comparative sample 8
           97.3WC/M-2.7Co    1,480
                                  95.5WC-4.5Co
Comparative sample 9
           93.0WC/M-7.0Co    1,420
                                  88.5WC-11.5Co
Comparative sample 10
           86.0WC/M-7.0Fe-5.0Ni-2.0Cr.sub.3 C.sub.2
                             1,420
                                  77WC-23(Fe--Ni--Cr)
Comparative sample 11
           89.2WC/M-2.1TaC-8.7Co
                             1,400
                                  83.5WC-2TaC-14.5Co
Comparative sample 12
           92.0WC/M-2.0TaC-6.0Co
                             1,440
                                  88WC-2TaC-10Co
Comparative sample 13
           73.0WC/M-20.0WTT-7.0Co
                             1,400
                                  63WC-26(W, Ti, Ta)C-11Co
Comparative sample 14
           46.6WC/M-40.0WTT-13.4Co
                             1,440
                                  37WC-45(W, Ti, Ta)C-18Co
Comparative sample 15
           76.9W.sub.2 C-20.0P(1)-3.1C
                             1,520
                                  97WC-3Co
Comparative sample 16
           72.7P(7)-23.0Co-4.3G
                             1,360
                                  57WC-43Co
Comparative sample 17
           51.3P(4)-47.0WTT-1.7C
                             1,440
                                  31WC-53(W, Ti, Ta)C-16Co
__________________________________________________________________________

                                  TABLE 3
__________________________________________________________________________
                   Fracture
                         Average
                              Ratio of
                                   Ratio of
           Flexural
               Hard-
                   toughness
                         particle
                              platy WC
                                   WC crys-
                                        WC lattice
                                                Axial
Sample     strength
               ness
                   value K1C
                         size of
                              (% by
                                   tal faces
                                        constant (nm)
                                                ratio
No.        (GPa)
               HV20
                   (MPa · m.sup.1/2)
                         WC (μm)
                              volume)
                                   001/101
                                        a axis
                                            c axis
                                                c/a
__________________________________________________________________________
Present sample 1
           2.7 1,750
                   10.3  1.5  about 70
                                   0.65 0.29084
                                            0.28412
                                                0.9776
Present sample 2
           3.6 1,590
                   13.6  0.3  about 80
                                   0.69 0.29082
                                            0.28422
                                                0.9778
Present sample 3
           2.8 1,700
                   10.9  1.5  about 60
                                   0.63 0.29085
                                            0.28419
                                                0.9776
Present sample 4
           3.5 1,270
                   --    1.6  about 80
                                   0.75 0.29084
                                            0.28418
                                                0.9776
Present sample 5
           2.6 1,380
                   14.3  1.4  about 40
                                   0.62 0.29086
                                            0.28415
                                                0.9773
Present sample 6
           3.1 1,370
                   15.5  3.2  about 60
                                   0.71 0.29082
                                            0.28415
                                                0.9777
Present sample 7
           2.8 1,620
                   11.1  0.4  about 70
                                   0.74 0.29085
                                            0.28421
                                                0.9779
Present sample 8
           1.7 2,110
                   7.8   1.8  about 40
                                   0.65 0.29084
                                            0.28420
                                                0.9775
Present sample 9
           2.9 1,890
                   9.8   1.3  about 60
                                   0.67 0.29082
                                            0.28414
                                                0.9774
Present sample 10
           2.7 1,870
                   9.7   1.4  about 50
                                   0.59 0.29084
                                            0.28412
                                                0.9776
Present sample 11
           2.6 1,610
                   12.6  1.6  about 60
                                   0.67 0.29085
                                            0.28419
                                                0.9776
Present sample 12
           2.6 1,780
                   10.0  1.4  about 70
                                   0.60 0.29082
                                            0.28415
                                                0.9777
Present sample 13
           2.4 1,950
                   8.9   1.4  about 50
                                   0.62 0.29086
                                            0.28415
                                                0.9773
Present sample 14
           2.2 1,890
                   8.5   1.5  about 60
                                   0.68 0.29082
                                            0.28422
                                                0.9778
Present sample 15
           2.4 1,900
                   8.6   1.4  about 70
                                   0.75 0.29084
                                            0.28420
                                                0.9775
Present sample 16
           2.0 1,870
                   8.7   1.4  about 50
                                   0.56 0.29084
                                            0.28412
                                                0.9776
Present sample 17
           2.2 1,540
                   10.7  1.6  about 70
                                   0.65 0.29082
                                            0.28414
                                                0.9774
Comparative sample 1
           2.5 1,650
                   9.4   1.5  about 0
                                   0.35 0.29063
                                            0.28378
                                                0.9764
Comparative sample 2
           3.3 1,470
                   11.2  0.3  about 0
                                   0.30 0.29061
                                            0.28377
                                                0.9765
Comparative sample 3
           2.6 1,640
                   10.1  1.4  about 0
                                   0.32 0.29065
                                            0.28382
                                                0.9765
Comparative sample 4
           2.1 1,180
                   --    1.5  about 0
                                   0.35 0.29070
                                            0.28390
                                                0.9765
Comparative sample 5
           2.7 1,300
                   12.9  1.5  about 0
                                   0.32 0.29066
                                            0.28382
                                                0.9765
Comparative sample 6
           2.9 1,270
                   14.5  3.1  about 0
                                   0.31 0.29067
                                            0.28385
                                                0.9764
Comparative sample 7
           2.6 1,540
                   10.1  0.3  about 5
                                   0.36 0.29062
                                            0.28378
                                                0.9767
Comparative sample 8
           1.8 2,090
                   7.1   1.9  about 5
                                   0.42 0.29060
                                            0.28376
                                                0.9766
Comparative sample 9
           2.7 1,800
                   8.9   1.4  about 0
                                   0.33 0.29062
                                            0.28377
                                                0.9767
Comparative sample 10
           2.3 1,520
                   8.9   1.5  about 0
                                   0.31 0.29061
                                            0.28374
                                                0.9764
Comparative sample 11
           2.5 1,700
                   9.0   1.3  about 0
                                   0.33 0.29066
                                            0.28382
                                                0.9765
Comparative sample 12
           2.2 1,830
                   8.0   1.5  about 0
                                   0.36 0.29061
                                            0.28377
                                                0.9765
Comparative sample 13
           2.0 1,810
                   7.8   1.5  about 0
                                   0.30 0.29065
                                            0.28382
                                                0.9765
Comparative sample 14
           2.0 1,470
                   9.7   1.5  about 0
                                   0.33 0.29062
                                            0.28378
                                                0.9767
Comparative sample 15
           1.2 2,010
                   6.8   2.0  about 40
                                   0.60 0.29063
                                            0.28378
                                                0.9764
Comparative sample 16
           2.9 1,070
                   --    1.6  about 70
                                   0.71 0.29060
                                            0.28376
                                                0.9766
Comparative sample 17
           1.7 1,640
                   8.7   1.5  about 60
                                   0.67 0.29069
                                            0.28390
                                                0.9765
__________________________________________________________________________
EXAMPLE 2
Green compact molds of Present samples 1, 6, 7, 9, 10, 11, 15 and 16 and Comparative samples 1, 6, 7, 9, 10 and 13 used in Example 1 were heated by the same method and under the same conditions as in Example 1, maintained at the respective temperatures of 950° C. and 1,100° C. for 5 minutes, cooled and then taken out. As to the heated compact molds, approximate compositions thereof were determined by the internal addition method by X-ray diffraction. The results are shown in Table 4.
                                  TABLE 4
__________________________________________________________________________
Sample     Compositional component during sintering under heating (% by
           weight)
No.        950° C.     1,100° C.
__________________________________________________________________________
Present sample 1
           35WC-25Co.sub.3 W.sub.9 C.sub.4 -20Co.sub.3 W.sub.3 C-20Co.sub.
           6 W.sub.6 C        75WC-20Co.sub.3 W.sub.3 C-5Co
Present sample 6
           30WC-30(W--Co)-20Co.sub.3 W.sub.3 C-20Co.sub.6 W.sub.6
                              60WC-40Co.sub.3 W.sub.3 C
Present sample 7
           70Ni.sub.2 W.sub.4 C-20(W--Cr)-10WC
                              55WC-40Ni.sub.2 W.sub.4 C-5(Ni--Cr)
Present sample 9
           40W.sub.2 C-30Co.sub.3 W.sub.3 C-20WC-10Co.sub.6 W.sub.6
                              80WC-15Co.sub.3 W.sub.3 C-5Co
Present sample 10
           40W-20WC-20Co.sub.3 W.sub.3 C-20Co.sub.6 W.sub.6 C
                              70WC-30Co.sub.3 W.sub.3 C
Present sample 11
           50(Fe, Ni, Cr)3W.sub.3 C-30WC-20Fe.sub.4 W.sub.2 C
                              80WC-20Fe.sub.3 W.sub.3 C-10(Fe--Ni--Cr)
Present sample 15
           30WC-30Co.sub.3 W.sub.3 C-20W-20(W, Ti, Ta)C
                              65WC-20(W, Ti, Ta)C-10Co.sub.3 W.sub.3
                              C-5Co
Present sample 16
           50WC-20Co.sub.3 W.sub.3 C-10Co.sub.6 W.sub.6 C-10(Ti,
                              55WC-30Co.sub.3 W.sub.3 C-15(W, Ti, Ta)C
Comparative sample 1
           91WC-9Co           91WC-9Co
Comparative sample 6
           90WC-10Co          90WC-10Co
Comparative sample 7
           90WC-10(Ni--Cr)    90WC-10(Ni--Cr)
Comparative sample 9
           93WC-7Co           93WC-7Co
Comparative sample 10
           86WC-14(Fe--Ni--Cr)
                              86WC-14(Fe--Ni--Cr)
Comparative sample 13
           73WC-20(W, Ti, Ta)C-7Co
                              73WC-20(W, Ti, Ta)C-7Co
__________________________________________________________________________
EXAMPLE 3
Mixed powders of Present samples 6, 7, 9 and 15 and Comparative samples 6, 7, 9 and 13 used in Example 1 were charged into metal molds each having a sectional shape of about 16×16 mm and pressurized under a pressure of 2 ton/cm2 by using upper and lower punches to prepare green compact molds each having a size of about 16×16×6.2 mm. The green compact molds were sintered under heating by the same method and under the same conditions as in Example 1.
The hard alloy samples thus obtained were subjected to wet grinding processing using #230 diamond grinding stone, and one face of the upper and lower faces (shown as "p face" in Table 5) and one face the side faces (shown as "h face" in Table 5) of the samples were subjected to lapping with 1 μm of diamond paste. As to the respective p faces and h faces, the peak intensity ratio of the (001) face to the (101) of the WC crystal by X-ray diffraction was measured. Further, as to the respective peak intensity ratios obtained, the ratio of the p face to the face was calculated. The results are shown in Table 5.
              TABLE 5
______________________________________
              Peak intensity
                            Face ratio of
Sample        ratio         peak intensity
No.          p face     h face  p/h
______________________________________
Present sample 6
             0.74       0.42    1.76
Present sample 7
             0.80       0.49    1.63
Present sample 9
             0.67       0.44    1.52
Present sample 15
             0.75       0.51    1.47
Comparative sample 6
             0.31       0.32    0.96
Comparative sample 7
             0.36       0.33    1.09
Comparative sample 9
             0.33       0.33    1.00
Comparative sample 13
             0.30       0.29    1.03
______________________________________
From the results shown in Tables 3, 4 and 5, it can be seen that the platy WC-containing hard alloys of the present invention exhibit flexural strength, hardness and fracture toughness all of which are higher than those of the comparative hard alloys comprising the same components.
As used in the following examples, the designations "FC350", "S48C" and "SKD11" have the following compositions.
__________________________________________________________________________
Components (% by weight)
Symbol
    C   Si  Mn  P    S    Cr  Mo  V   Cu Fe
__________________________________________________________________________
SKD11
    1.40˜
        0.40 or
            0.60 or
                0.030 or
                     0.030 or
                          11.00˜
                              0.80˜
                                  0.20˜
                                      -- Re-
    1.60
        less
            less
                less less 13.0
                              1.20
                                  0.50   mainder
S48C
    0.45˜
        0.15˜
            0.60˜
                0.030 or
                     0.035 or
                          --  --  --  -- Re-
    0.51
        0.35
            0.90
                less less                mainder
FC350
    2.5˜
        0.5˜
            0.3˜
                0.01˜
                     0.02˜
                          0.1˜
                              --  --  0.1˜
                                         Re-
    4.0 3.0 1.2 0.6  0.12 0.5         1.0
                                         mainder
__________________________________________________________________________
EXAMPLE 4
Mixed powders of Present samples 9 and 13 and Comparative samples 9 and 12 used in Example 1 were charged into metal molds each having a sectional shape of about 16×16 mm and pressurized under a pressure 2 ton/cm2 by using upper and lower punches to prepare green compact molds each having a size of about 16×16×6.2 mm. The green compact molds were sintered under heating by the same method and under the same conditions as in Example 1 and then subjected to wet grinding processing to obtain chips for cutting of SNGN120408 according to ISO Standard. As to these chips, a lathe turning test was conducted by using molds under the following conditions to measure a lift time until a flank wear amount became 0.35 mm. The results are shown in Table 6.
Material to be cut: FC350
Cutting rate: V=100 m/min
Depth of cut: d=1.5 mm
Feed: f=0.3 mm
Processing liquid: dry type
EXAMPLE 5
Mixed powders of Present samples 12 and 15 and Comparative samples 11 and 13 used in Example 1 were charged into metal molds each having a sectional shape of about 16×16 mm and pressurized under a pressure of 2 ton/cm2 by using upper and lower punches to prepare green compact molds each having a size of about 16×16×6.2 mm. The green compact molds were sintered under heating by the same method and under the same conditions as in Example 1 and then subjected to wet grinding processing to obtain chips for cutting of SNGN120408 according to ISO standard. These chips were subjected to pre-horning at -30°×0.15 mm and then charged into a CVC coating furnace. The surfaces of the chips were coated successively with 1.0 μm of TiN, 5.0 μm of TiCN, 2.0 μm of TiC, 2.0 μm of Al2 O3 and 1.0 μm TiN (total coating thickness: 11 μm). By using the coated chips obtained, an intermittent lathe turning test was conducted by using steel under the following conditions to measure a life time until a blade tip was broken or a flank wear amount became 0.35 mm. The results are shown in Table 6.
Material to be cut: S48C (with 4 grooves)
Cutting rate: V=150 m/min
Depth of cut: d=2.0 mm
Feed: f=0.25 mm
Processing liquid: dry type
EXAMPLE 6
Mixed powders of Present sample 2 and Comparative sample 2 used in Example 1 were pressurized under a pressure of about 2 ton/cm2 by using a dry hydrostatic pressure press device to prepare round bar molds each having a diameter of 10 mm and a length of 56 mm. The round bar molds were sintered under heating by the same method and under the same conditions as in Example 1 and then subjected to wet grinding processing to obtain end mills each having a length of 42.0 mm, a blade tip diameter of 6.0 mm, a blade number of 2 and a helix angle of 30°. As to these end mills, a cutting processing test was conducted by using metal mold steel under the following conditions to measure a life time until a flank wear amount became 0.25 mm. The results are shown in Table 6.
Material to be cut: SKD11
Cutting rate: V=45 m/min
Depth of cut: d=6.0 mm
Feed: f=0.02 mm/blade
Width of cut: W=3.5 mm
Processing liquid: wet type (a water-soluble oily agent)
EXAMPLE 7
Mixed powders of Present samples 3 and 7 and Comparative samples 3 and 7 used in Example 1 were pressurized under a pressure of about 2 ton/cm2 by using a dry hydrostatic pressure press device to prepare cylindrical molds each having an outer diameter of 52 mm, an inner diameter of 12 mm and a height of 40 mm and round bar molds each having a diameter of 14 mm and a length of 40 mm. The cylindrical and round bar molds were sintered under heating by the same method and under the same conditions as in Example 1 and then subjected to wet grinding processing to obtain dies each having an outer diameter of 40.0 mm, an inner diameter of 10.00 mm and a height of 30.0 mm and punches each having a diameter of 9.95 mm and a length of 30.0 mm. By using molds comprising a combination of the die and the punch of the same alloy among the dies and punches obtained, a press molding test was conducted by using powder under the following conditions to measure a life time until flashes were formed on the mold. The results are shown in Table 6.
Powder to be molded: ferrite
Size of mold: diameter: 10.0 mm, thickness: 2.0 mm
Molding time: 1 second
Molding cycle: 5 seconds/mold
Molding pressure: 3 ton/cm2 
              TABLE 6
______________________________________
Test item Sample No.     Life time
______________________________________
Lathe turning
          Present sample 9
                         27 minutes
of mold   Present sample 13
                         34 minutes
(Example 4)
          Comparative sample 9
                         15 minutes
          Comparative sample 12
                         20 minutes
Intermittent
          Present sample 12
                         18 minutes
cutting of
          Present sample 15
                         25 minutes
steel     Comparative sample 11
                          7 minutes
(Example 5)              (abnormal wear by
                         plastic deformation)
          Comparative sample 13
                         12 minutes
                         (chipping wear)
Cutting proces-
          Present sample 2
                         25 minutes
sing of metal
          Comparative sample 2
                         17 minutes
mold steel               (chipping wear)
(Example 6)
Press molding
          Present sample 3
                         324 hours
(Example 7)
          Present sample 7
                         517 hours
          Comparative sample 3
                         178 hours
          Comparative sample 7
                          15 hours
                         (fracture occurred)
______________________________________
The hard alloy containing platy WC of the present invention has remarkably excellent effects in that it has a Vickers hardness of 500 or more at HV20 and a fracture toughness K1c of 0.5 MPa·m1/2 or more as compared with a conventional hard alloy having the same composition and particle size. The process for preparing the same has effects in that a hard alloy having a high content of platy WC and a controlled particle size can be prepared easily and inexpensively.
Further, the beneficial effects of the hard alloy containing platy WC of the present invention can be expected when a covered hard alloy is prepared by covering the surface of the hard alloy of the present invention with a hard film comprising a single layer or a multilayer of at least one of carbide, nitride, oxycarbide and oxynitride of the 4a (Ti, Zr and Hf), 5a (V, Nb and Ta) or 6a (W, Mo and Cr) group element of the periodic table, oxide and nitride of Al and mutual solid solutions thereof, diamond, diamond-like carbon, cubic boronitride and hard boronitride.

Claims (6)

We claim:
1. A process for preparing a plate-crystalline tungsten carbide-containing hard alloy which comprises 4 to 40% by volume of a binder phase containing at least one of iron group metals selected from Co, Ni and Fe; and the balance of a hard phase comprising tungsten carbide alone, or tungsten carbide and 50% by volume or less of a compound with a cubic structure selected from at least one of carbide and nitride of an element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W and mutual solid solutions thereof, which comprises the steps of:
(A) heating (i) at least one of cobalt, nickel, iron and chromium, (ii) tungsten and (iii) carbon, or a precursor thereof to form a solid-solution compound;
(B) mixing:
(1) the solid solution formed in (A), and
(2) a carbon source compound of at least one of carbon, graphite and carbon precursors thereof, or said carbon source compound and a composition-adjusting compound comprising at least one of carbide and nitride of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten and mutual solid solutions thereof, and cobalt, nickel, iron and chromium and mutual alloys thereof, to prepare mixed powder;
(C) molding said mixed powder into a molded compact; and
(D) sintering said molded compact under heating at 1,200 to 1,600° C. under vacuum or non-oxidizing atmosphere.
2. A process according to claim 1, wherein said solid solution compound is at least one solid solution compound selected from the group consisting of Co3 W9 C4, Co2 W4 C, Co3 W3 C, Co6 W6 C, Ni2 W4 C, Fe2 W4 C, Fe3 W3 C, Fe4 W2 C and mutual solid solutions thereof.
3. A process according to claim 1, wherein the precursor of the solid solution compound is a mixed powder of (i) at least one selected from the group consisting of a tungsten-containing alloy, tungsten, ditungsten carbide and tungsten oxide; and (ii) at least one of cobalt, nickel, iron and chromium.
4. A process according to claim 1, wherein the precursor of the solid solution compound is a mixed powder of tungsten carbide and at least one selected from the group consisting of oxides of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium and molybdenum.
5. A process as claimed in claim 1, wherein the carbon source compound has a particle size of 0.2 μm to 20 μm.
6. A process for preparing a plate-crystalline tungsten carbide-containing hard alloy which comprises 4 to 40% by volume of a binder phase containing at least one of iron group metals selected from Co, Ni and Fe; and the balance of a hard phase comprising tungsten carbide alone, or tungsten carbide and 50% by volume or less of a compound with a cubic structure selected from at least one of carbide and nitride of an element selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W and mutual solid solutions thereof, said process comprising the steps of:
(A) mixing
(1) plate-crystalline tungsten carbide-forming powder which comprises:
(a) a component comprising at least one of cobalt, nickel, iron and chromium, and
(b) at least one of tungsten, tungsten-containing alloy, ditungsten-carbide, tungsten oxide, and tungsten carbide with at least one element selected from the group consisting of oxides of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, and molybdenum, and
(2) a carbon source compound of graphite and carbon precursors thereof, or said carbon source compound and solid solutions thereof to prepare mixed powder, wherein said carbon source compound has an average particle size of 6 to 20 μm;
(B) molding said mixed powder into a molded compact; and
(C) heating said molded compact under hating at 1,200 to 1,600° C. under vacuum, whereby during heating a composite carbide is first formed, followed by sintering to form the tungsten carbide-containing hard alloy.
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